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Патент USA US3082189

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United States Patent 0
1
1C6
I
3,082,180
Patented Mar. 19, 1963
2
3,082,180
unlimited range or form of artistic effects so long as the
inks of the coloring matter contained therein are non
‘ FOR DECORATIVE LAMINATING AND PROC
ESS FOR PREPARING SAME
>
bleeding in the resin comprising the infused resin compo
nent of the print sheet or that of the subsequently applied
MODXFIED MELAMINEJFORMALDEHYDE RESIN
Leslie Boldizar, Wallingford, and Lewis C. Pounds,
Cheshire, Conrn, assignors to American Cyanannd
Company, New York, N.Y., a corporation of Maine
No Drawing. Filed Oct. 4, 1960, Ser. No. 60,322
9 Claims. (Cl. 26t)--17.3)
overlay sheet; The print sheet also serves as ‘a barrier
sheet for the core stock member, thus masking the un
attractive appearance of the core stock and additionally
‘barring any extensive bleeding or migration of the phe
nolic resinous material contained thereby that otherwise
l0 might be apparent on the decorative surface of the lami
This invention relates to novel, modi?ed aminoplast
nate. The print sheet is required to have good appear
resinous compositions, to products prepared therefrom,
ance and’durability. These properties are conventionally
andto methods of producing such compositions and prod
ucts. More particularly, this invention relates to novel,
achieved by impregnating the print sheet with an amino
modi?ed aminoplast resinous compositions possessing
Whether they comprise unmodi?ed or modi?ed conden
sates, are constituted to impart color stability and resist
properties which render them particularly useful in the
preparation of decorative laminates.
The aminoplast resinous compositions which are modi
plast resinous composition.
The aminoplast resins,
ance to discoloration and degradation due to heat and
light to the print sheet, and also to impart hardness and
?ed in accordance with our inventioin are resinous reac- .
resistance to abrasion, solvents and chemicals to the over
tion products of ingredients comprising an aldehyde, e.g., 20 lay, or to the print sheet if no overlay is used. In addi
formaldehyde and an aminotriazine containing at least 2
amidogen groups, each having at least one aldehyde're~
actable hydrogen atom attached to the amidogen nitrogen
atom, e.g., melamine. We have found that modi?cation
of this resinous reaction product in the manner more fully 25
described hereinbelow produces improved aminoplast
resinous compositions which, when used in laminating as
semblies, result in ?nal products having improved post
forming characteristics together with surface areas ex
hibiting a high degree of heat and chemical resistance.
tion, the aminoplast resins give a thorough impregnation,
thereby insuring a complete bond in the laminate.
Because of the excessive wear to which decorative
laminate surfaces, especially horizontal working surfaces
such as table tops, are generally subjected, it is conven—
tional practice in this art to lend greater durability to the
laminate structure by applying an overlay sheet over the
print sheet. The overlay sheet, often-times called the
decorative overlay, usually consists of a single sheet of
paper, generally a very high grade of int-cellulose paper,
treated with an aminoplast resinous composition more
often than not corresponding to that used to impregnate
rected involves the preparation of‘ decorative, resin-bonded
the print sheet member of the assembly. The primary '
multilayer structures commonly referred to as laminates,
objective in the use of the overlay sheet is to impart dura
and more speci?cally high pressure laminates, wherein a 35 bility to the print sheet without detracting from its appear
thermosetting aminoplast condensate is employed to im
ance. As mentioned, the aminoplast resins are favored
pregnate the decorative portions thereof. Such structures
for impregnating the overlay sheet because of their afore
are exempli?ed by those laminated articles intended to be
mentioned desirable properties, and when thus employed
The end use to which the novel, modi?ed aminoplast
resinous compositions of this invention are principally di
used as horizontal or working surfaces, e.g., table, coun- '
are present therein in a very substantial amount. The
ter and bar tops. Additionally, such structures are often 40 resin content of the overlay sheet is customarily between
times employed as wall coverings, facings for kitchen
about 60% and 70% of the treated sheet. In comparison,
cabinet assemblies and the like.
the conventional‘ resin content of the print sheet is in
In laminated‘ articles of the type involved herein, the
the order of about 40% to 50% of the treated sheet and
core is conventionally composed of a plurality of kraft
the resin content of the core sheets ranges from about
paper plies which have been impregnated with a phenolic
25% to 35% of said treated sheets. The conventional
resin, e.g., a resin obtained by reacting a‘ phenolic sub
decorative laminates are usually from about 50 to 60 mils
stance such as phenol itself; substituted phenols, e.g., the
alkyl phenols, such as the cresols, the xylenols, the ter
tiary alkyl phenols; and the like, with an aldehyde such
as formaldehyde, acetaldehyde, propionaldehyde, benz~
aldehyde, furfural, etc; with mixtures'thereof, or with
thick. Of this thickness the overlay sheet represents
about 2 to 4 mils, the print sheet is conventionally in
the order of about 5 to 9 mils and the core member
constitutes the rest of this assembly.
When a conventional decorative laminate assembly is
cured under the usual applicable pressures, that is, from
mixtures of one or more of such aldehydes and substances
such as urea, thiourea, substituted ureas and thioureas,
about 800 to 1500 p.s.i., the curing is effected at a tem—
aminotriazines, such as melamine; and the like, which-ex
perature'range wherein the-aminoplast resin as Well as
state. The function of the core is to impart rigidity to the
laminated structure. Insofar as this part of the laminate
cannot be seen and additionally since this part is not sub
jected to abrasive conditions, the core is customarily fab
complete curing is from about 135° C. to 145 ° C. The
time required at a temperature within this range is in the
ists infused throughout the individual plies in an uncured 55 the phenolic resin present is regarded as being completely
cured. The usual temperature range employed to effect
order of approximately 20 minutes although for all con
ricated from relatively inexpensive materials. Suitable 60 ventional unmodi?ed aminoplast resins, a period anywhere
core Stock members are prepared using a low cost kraft
from about 5 minutes shorter or longer can be tolerated.
paper together with the least amount of a phenolic resin
capable of providing a good bond for the core assembly.
When cured under the stated conditions the laminate,
and particularly the surface area thereof, will be rendered
highly resistant to heat, that is, objects at temperatures
A so-called print sheet supplies the decorative effect
associated with the laminate, and in preparing the as 65 ranging as high as about 180° C. may be placed on the
surface of the laminate for as long as 20 minutes without
sembly for lamination, it is placed on topof the sheets
any visible effect upon the plastic. Also such a composite
constituting the core member. The print sheet generally
cured to a point Where it exhibits adequate heat resistance
consists of a pu-regrade of an absorbent Ct-CCilUlOS? or
regenerated cellulose paper which has been printed with 70 in the nature described will also manifest excellent chemi
cal resistance.
a design or dyed or pigmented to impart a solid color
thereto.
Printed designs may be employed having an
Aminoplast resinous compositions previously employed‘
in the production of decorative laminates have not been
3,082,180
3
4
entirely satisfactory, however, inasmuch as the resins ex
radius of MW-Vz” at its apex. Present NEMA (Na
tional Electrical Manufacturers Association) Standards
hibit stitf ?ow at the usual operating temperatures. Var1~
ous modi?ers have been incorporated into these resins to
cal for a bend having a right angle with a radius of
3/4” or less at its apex.
improve their plastic ?ow characteristics during cure,
Laminators are continually trying to approach the
and other modi?ers have been utilized to improve di
mensional stability and workability or to impart any num
ber of additional desirable properties to the cured resins.
Many of the modi?ers that have been employed in the
ideal radius and at the same time retain the excellent
physical properties of the original aminoplast laminate,
and several attempts to obtain such improved post
formable decorative aminoplast laminates have been
aminoplast resins contribute undesirable characteristics 10 practiced in the prior art with varying degrees of suc
to the resinous compositions during the preparation of the
cess. One such method consists of somewhat undercur
ing the entire laminating assembly during lamination.
laminate. For example, certain modi?ers, when incorpo
rated into the resinous syrup, produce an unstable com
While this method permits the assembly to be post
position. Also, in certain instances the resinous composi
formed, the heat and chemical resistance of the resulting
tion, after impregnation and during drying has a tendency
article are unsatisfactory. In addition, such post-formed
prior art to enhance the physical properties of the cured
As a result, the drying of the impregnated
laminates develop a dull surface appearance in the area
paper must be carried out at an uneconomical rate in
to froth.
surrounding the line where the shaping or bending force
is applied. In general, these de?ciencies inhere in most
of the prior art attempts to prepare satisfactory post
order to avoid this frothing.
A further dit?culty inherent in prior art aminoplast
resinous compositions used in the preparation of deeora- ..
formable decorative aminoplast laminates.
tive laminates is the above-mentioned phenomenon of
“bleeding.” When an aminoplast resin-impregnated deco
rative overlay or print sheet is used in combination with
novel, modi?ed aminoplast resinous compositions.
a core assembly impregnated with a different thermo
modi?ed aminotriazine-aldehyde resinous compositions,
It is, therefore, an object of our invention to prepare
It is also an object of our invention to prepare novel,
setting resinous composition, e.g., a phenol-formaldehyde
and particularly, melamine-formaldehyde resinous com
resin, there is a tendency for the resin material of the
positions, which will overcorne the aforementioned de?
ciencies in prior art decorative laminates and permit
laminates prepared therefrom to be converted into post
core assembly to migrate into the print sheet, producing
discoloration on exposure of the laminate to light. By
using an increased aminoplast resin content in the print
formed shapes having right angles with radii of WNW-SA"
or overlay sheet, the tendency of the core assembly to 30 at their apexes While retaining good heat, abrasion,
migrate is reduced. However, the use of increased
solvent and chemical resistance and good surface ap
pearance.
amounts of aminoplast resin su?icient to achieve the
desired purpose may be considered uneconomical for most
These and other objects of our invention are accom
practical purposes.
But by far the most serious defect possessed by prior
art aminoplast resin-containing laminates assembled and
35
plished by modifying a resinous reaction product of in
gredients comprising (a) an aminotriazine containing at
least 2 amidogen groups, each having at least one alde
cured in the manner described above lies in the fact that
hyde-reactable hydrogen atom attached to the amidogen
they cannot be post-formed to any appreciable extent, for
nitrogen atom, e.g., melamine and (b) an aldehyde, e.g.,
when post-forming is attempted, such laminates readily 40 formaldehyde with a three-component modi?er system
crack.
comprising (0) an a-alkyl~D-glucoside, e.g., a-methyl-D~
“Post-formability” refers to the ability of a laminated
glucoside, (d) an N-methylol sulfonamide, e.g., N-meth~
sheet to be bent without cracking to form a right angle
having a narrow are at its apex.
This property is im-.
ylol-toluene sulfonamide, and (a) one or more amines, in
certain prescribed quantities, as will be set forth more
portant for both functional and decorative purposes. For 45 fully hereinbelow.
example, in the manufacture of table tops having con
As is well known, aminoplast resins are synthetic
toured edges or in the preparation of sink working areas
resins prepared by the condensation reaction of an amino
where the splash appendage is desirably an unbroken con
(including imino) or amido (including imido) compound
tinuation of the horizontal surface, it may be desirable to
with an aldehyde, a typical example being melamine
50
post-form the shape of the decorative laminate as re
formaldehyde resins. Aminoplast resins of the type
ceived from the fabricator thereof. While it is possible
which may be modi?ed in accordance with the present
for the laminator to achieve any size flat sheet desired
invention are produced by techniques well known in the
during the manufacture of the laminate, it is virtually
art, as shown, for example, in U.S. Patent No. 2,197,357
impossible for him to produce the multiplicity of particu 55 to Widmer et al., and in U.S. Patent No. 2,260,239 to
lar contoured shapes and custom designs required by
Talbot. The mol ratio of aldehyde to aminotriazine in
individual customers. Thus, there is an important need
such resinous compositions is not critical, and may be
for high pressure laminates which may be shaped “on the
within the order of from about 1.521 to about 6:1, re
job” and yet conform to the high standard of physical
spectively, depending on the nature of the starting ma
properties ordinarily associated with such articles.
60 terials and the characteristics desired in the ?nal prod
In standard post-forming procedures, the laminate is
ucts, but it is preferred that the mol ratio be within the
heated along the line to be formed, and then bent to the
order of from about 2:1 to about 4:1, respectively.
desired angle. There are many kinds of post-forming
We prefer to use those partially polymerized aldehyde
equipment, but essentially the preheated laminate is bent
aminotriazine resins which are heat curable or potentially
around a bar to a right angle having a radius of from 65 heat curable resinous reaction products of ingredients
%"-1" at the apex of the bend, and then allowed to
comprising melamine and formaldehyde. However,
cool somewhat before being removed from the post
other heat curable or potentially heat curable partially
forming apparatus in order to overcome any tendency of
polymerized aldehyde-aminotriazine resinous reaction
the laminate to “spring back” to its original shape.
products may also be employed. Aminotriazincs con
Ideally, the resin binder in a post-formable laminated 70 taining at least two amidogen groups, each having at least
sheet should be capable of being cured to the stage at
one aldehyde-reactable hydrogen atom attached to the
which it is sutticiently heat resistant and yet ?exible
amidogen nitrogen atom, which may be reacted with an
enough when exposed to heat in the post-forming opera
aldehyde to provide the resin which is modi?ed in ac
tion so as to give a bend having a right angle with a
cordance with our invention include, among others, the
3,082,180
5
6
triamino-s-triazines represented by the structural for
' form properties could not be obtained in each instance.
mula:
By the employment of the ot-alkyl-D-glucosides, as here
in set forth, wherein the lactol ring is de?nitely ?xed,
uniformly improved properties are insured in the modi
?ed composition. Not only is this component of the
modi?er utilized in the present invention relatively in
expensive, it is also water white, and when incorporated
into the resinous composition yields a composition that
is also water white and has excellent color stability. It
10
wherein any of R1 to R6 may be hydrogen, alkyl, cyclo
has been previously suggested that a-alkyl-D-glucosides
alkyl, alkenyl, cycloalkenyl, aryl, aralkyl, alkaryl, hy~
be incorporated into alkylated aminoplast resins for cer
tain purposes. In the present case the aminoplast resins,
droxyalkyl, amino or substituted amino (e.g., alkylamino,
dialkylamino, etc.), with the proviso that in at least two
of the amidogen substituents directly attached to the car—
speci?cally melamine-formaldehyde resins, which are
herein modi?ed are substantially non-alkylated. As is
well known, alkylated melamine-formaldehyde resins are
obtained by reacting the melamine-formaldehyde con
bon atoms of the triazine nucleus at least one R is hydro~
gen.
An illustrative but by no means exhaustive enu~
densation product in the presence of a compound con
meration of such an1ino~s~trinzines includes the following:
taining an alcoholic hydroxy group whereby the methylol
2~mono~R~amino-4,6~diamino-s-triazines such as the N
derivative of the condensation product reacts with the al
methyl, N-butyl, N-phenyl, N~tolyl and N-cyclohexyl
coholic hydroxy group of the modifier. The alkylated
and non-alkylated melamine-formaldehyde condensation
melamines; 2,4,6-tris (mono-R-amino)~s~triazines such as
2,4,6-tris (methylamino)-s-triazine; 2-di~R-amino-4,6-bis
products are physically and chemically distinct. In pre
(mono-R-amino)-s-triazines such as 2-dimethylamino-4,6
paring the modi?ed resinouscompositions of the present
invention, any alkylation is incidental and occurs only
bis (methylamino)-s—striazine; the methylolmelamines,
such as mono-, di-, and trimethylolmelamines, Ng-dimeth
as a result of the solvent used, if present, during the for
mation of the condensation product such as, for exam
ylol-N‘t, N‘i-bis (methylol)-mclamine; hydrazino-s-tria
zines, such as 2,4,6-trihydrazino-s-triazine; and the like.
Another suitable class or" 'aminotriazines comprises the
diamino-s-triazines represented by the structural for
ple, small amounts of methanol which may be present
in the aqueous formaldehyde solution.
The second component of the modi?er employed in the
30 preparation of the novel compositions of the present in
vention is an N-rnethylol sulfonamide of the general for~
mula:
Y
‘
35
1'1
R—SO2-N—CIlz-OH
wherein R represents an organic radical, e.g., alkyl, aryl,
alkaryl or aralkyl and R1 represents hydrogen, alkyl, al—
wherein each of R1 to R4 have the same meaning as
given above and in which X is hydrogen, hydroxy, alkyl,
kylol, aryl or an acyl group.
These compounds may be
- produced in any suitable manner, such as by the reaction
cycloalkyl, alkenyl, cycloalkenyl, aryl,_"aralkyl, alkaryl,
40 of a sulfonyl chloride with a rnethylol amine, or by the
or hyclroXyalkyl, again with the proviso that in each of
the amidogen substituents directly attached to the carbon
atoms of the triazine nucleus at least one R is hydrogen.
Illustrative of this class of s-triazines are the following:
methylolation of a sulfonarnide with formaldehyde e.g.,
in situ. Examples of such N-niethylol sulfonarnides in
clude N-methylol-toluene sulfonamide, N-methylol-p-cy
guanamines, such as formoguanamine, acetoguanamine, L
capryloguanamine, methacryloguanamine, sorboguana
mine, adipoguananiine, sebacoguanamine, ns-tetrahydro
benzoguanamine, hexahydrobenzoguanamine, benzoguan
amine, phenylacetoguanamine, diphenyladipoguanamine;
mene sulfonamide, N-methylol-xylene sulfonamide, N
methylol-tetralin sulfonamide, N,N’-dimethylol-toluene
disulfonamide, N,N'-dimethylol-diphenyl disulfonarnide,
and the like.
’
-
N-methylol sulfonamide modi?ers as herein de?ned
have previously been suggested for incorporation in
ammeline, and the like.
50 melamine-formaldehyde condensation products, for exam»
Any suitable aldehyde may be utilized as a reactant
ple, see US. Patent No. 2,326,728 to Schroy. The resin- _
with the aminotriazine in preparing the aminoplast resin.
ous compositions prepared in accordance with the above—
We prefer to employ formaldehyde, either as such or as
identi?ed patent, while solving a particular problem,
an aqueous solution.
Other aldehydes such as, for exam
ple, acetaldehyde, propionaldehyde, butyraldehyde, benz~
aldehyde, furtural; mixtures thereof, or mixtures of form
aldehyde with other such aldehydes may be employed.
Paraformaldehyde, hexamethylenetetramine, trioxymeth
ylene, paraldehyde, or other compounds engendering al
dehydes may also be employed.
The properties desired in the ?nished product and
economic considerations are among the features which
will determine the choice of the particular aldehyde and
aminotriazi-ne employed.
.
As previously stated, thelmodi?er employed in accord
ance with the present invention is a three~component
system. One component of the modifier system is an
a-alkyhD-glucoside in which the alkyl group may con
tain from one to four carbon atoms, such as a-methyl-D
glucoside, a-ethyl-Dglycoside,‘ a-‘butyl-Dglucoside and,
the like. Prior to the present invention, aminoplast
resins have been modi?ed by the addition of various
sugars, such as sucrose, lactose, glucoseand the like.
However, due to the many possible isomeric and mute
meric forms of these sugars, compositions possessing uni~
nevertheless present certain disadvantages when employed
55 in the production of laminated articles.
It was found
necessary to incorporate large amounts ‘of alcohol into
the solvent in order to obtain a soluble or dispersible
syrup or varnish that could be employed for impregna
tion of the laminating sheets. It was also found that the
60 resinous syrups or varnishes thus produced had limited
stability. Also, when it was desired to dry impregnated
laminating sheets rapidly at elevated temperatures, i.e.,
under typical conditions employed when utilizing modern
‘impregnation means, the treated laminates had a tendency
to ?ake, frost, and blister, resulting in resin impregnated
laminating sheets that were di?icult to handle.
Byremploying the novel three-component modifying
system as herein set forth and described, the disadvantages
previously experienced are reduced. Also, the amount of
alcohol necessary in the solvent in order to obtain a solu
tion or dispersion of the resinous compositionis greatly
reduced. This not only aids in eliminating the frothing
problem but also reduces ?re hazards which always ac
company .the use of solvent systems containing large ‘,
amounts of alcohol. Furthermore, impregnation may be
3,082,180
8
carried out at high speeds to give laminating sheets which
are thoroughly wet throughout. In addition to these fac
tors, it has been found that the tendency towards bleeding
of the resinous composition of the core assembly is sub
stantially reduced.
The ability possessed by laminates prepared from our
novel, modi?ed aminoplast resinous compositions to be
converted into post-formed shapes having right angles
with radii of -";’1t;"-%” at their apexcs is believed to be
ing from about 0.5 atom to about 10 atoms of basic nitro
gen present in the polyfunctional aliphatic polyamine per
mol of melamine, i.e., at least 10% by weight) in the
presence of an acid, modi?ed resin compositions are ob
tained which are particularly useful as wet strengthening
agents for paper. However, these patents re?ect no ap
preciation of either the three-component modi?er system
employed in the practice of the present invention or of the
use of very small amounts of such amine modi?ers, both
particularly due to the amine constituent of the three 10 of which features must be observed in order to obtain
aminoplast resinous compositions which will impart good
component modi?er system employed in accordance with
post-forming properties to laminates prepared therefrom.
the present invention, although the overall improvements
The total amount of a-alkyl-D-glucoside and N-meth
in physical and chemical properties resulting from the
ylol sulfonamide incorporated into the aminott'iazinealde
remaining components of the modi?er system also con
15 hyde condensate in accordance with the present invention
tribute to this effect.
The alkylene polyamines, including the polyalkylene
may be within the order of from about 1% to about 35%
polyamines, constitute the preferred class of amines which
by weight, based on the total weight of modi?ed resinous
composition (aminotriazine-aldchyde resin plus modi
may be employed as modi?ers in the practice of our in
fiers), but it is preferred that the total amount of these
vention. 3,3’-iminobispropylamine is especially suitable,
but other alkylene pclyamincs such as, for example, di 20 two modi?ers employed be within the order of from about
10% to about 30% by weight, based on the total weight
ethylene triamine, triethylene tetramine, tetraethylene pen
of the resinous composition. The amount of a-alkyl-D
tamine, tris-(3-aminopropyl)amine, ethylene diamine, tri
glueoside employed may range from about 0.5% to about
methylene diamine, tetramethylene diamine, propylene di
34.5% by weight, and correspondingly, the amount of
amine (1,2-diaminopropanc), and mixtures thereof, may
also be employed.
Our invention is not limited to the use of the above
mentioned polyamincs. A wide variety of other amines
or mixtures of amines may also be employed. For exam
ple, we may use primary, secondary or tertiary amines
N-methylol sulfonmide may vary from about 34.5% to
about 0.5% by weight, based on the total weight of the
resinous composition. For certain applications, it will be
desirable to employ a preponderance of a-alkyl-D-gluco
side, whereas in other applications it may be desired to
in which the amino group is attached to a primary, 30 incorporate a greater amount of the N-n'icthylol sulfona~
secondary or tertiary aliphatic carbon atom. Such amines
may have as substituents hydrocarbon radicals, e.g., alkyl,
mide. For optimum results, however, it is preferred that
isoalkyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, and alka
of from about 40:60 to about 60:40, respectively.
ryl radicals which may also contain hydrocarbon, sub
The amount of amine modi?er added may vary from
about 0.0 % to about 5%, based on the total weight of
stituted hydrocarbon and non-hydrocarbon substituents;
heterocyclic or substituted heterocyclic radicals, and vari
ous combinations thereof. Speci?c examples of such
amines include methylamine, isopropylamine, Z-amino
butane, t-butyl amine, 2-amino-4-methy1pentane, various
amyl, hexyl, heptyl, octyl and higher homologous pri
mary amines wherein the amine group is attached to a
primary, secondary or tertiary carbon atom; cyclopentyl
amine, alkylated cyclopentyl amines, cyclohexylarnine,
mono-, di- and trimethyl cyclohexylamines, other alkyl
ated cyclohexylamines; benzylamine, ?-phenylethylamine,
alkylated benzylamines, tetrahydro-{i-naphthylamine; di
methyl-, di-ethyl-, di-n-propyl-, di-isopropl-, and di-butyl
amine; various secondary amines derived from amyl,
hexyl, heptyl, octyl, and higher homologous alkyl groups,
methyl isobutyl amine, N-methyl-N-t-butyl amine, N
alkyl-N-cyclohexyl amines, N-alkyl-N-benzyl amines, and
their homologs and analogs; dicyclopentyl amine, dicyclo
hexyl amine, alkylated dicyclohexyl amines; diphenyl
amine, dibenzylamine, di-(?-phenylethyl)amine; trimeth
yl-, triethyl-, tri-n-propyl-, tri-isopropyl-, and tributyl
'amine, higher homologous and isomeric trialkylamines;
various N~substituted tertiary amines having different or
ganic radicals on the amine nitrogen atom, e.g., alkyl,
the weight ratio of these two modi?ers be within the order
the modi?ed resinous composition, depending on the
basicity of the particular amine or mixture of amines em
ployed. In the case of the alkylene polyamines, the
amount added will be within the range of from about
0.1% to about 1.5%, by weight.
In preparing the novel, modi?ed aminotriazincaldehyde
condensates of this invention, the aldehyde and amino
triazinc are heat-reacted, e.g., at temperatures ranging
from about 40° C. to about rc?ux temperature, i.e., about
100° C., for periods of time ranging from about 30 min
utes to about 120 minutes, either alone or in the presence
of a suitable solvent, such as water or a mixture of water
and a lower aliphatic alcohol.
_ The N-rnethylol sulfonamide modi?er may be formed
11'! situ during the condensation reaction of the aldehyde
and aminotriazine, e.g., by the methylolation of a sulfon~
amide, such as toluene sulfonamide, with formaldehyde,
or, alternatively, this modi?er may be separately formed
and then introduced into the aminotriazine-aldchydc com
position (when it is desired to form the N-methylol sul~
fonamidc in situ during the condensation reaction of the
aminotriazine and aldehyde, it is necessary that an excess
molar proportion of the aldehyde be present equal to the
alicyclic, aralkyl and like homologs and analogs; alkylol 00 molar proportion of the compound that forms the meth
ylol derivative). In any event, it is necessary that the
and alkyl alkylol amines such as ethanolamine, propanol
Nmiethylol sulfonamide be introduced into the amino
amine, diethanolamine, triethanolamine, methylmethanol
amine, rnethylethanolarnine, ethylmethanolamine, dimeth
triazine-aldehyde composition while said composition is
ylmethanolamine, dimethylethanolamine, diethylethanol
amine, dimethylpropanolamine, methyldimethanolamine,
ethyldiethanolamine, propyldimethanolarnine; heterocy
in a liquid state, inasmuch as it appears that amino
triazine-aldehyde condensates react with the N-methylol
sulfonamides.
if desired, the a-alkyl-D-glucoside may also be intro
duced into the aminotriazine-aldehyde composition during
cylie amines such ‘as piperidine, alkylated piperidines,
morpholine, and the like.
Compounds of the type set forth above have previ
the condensation reaction. Alternatively, the condensa
ously been utilized as modi?ers for melamine-formalde 70 tion product may be dried by any conventional method,
such as by pan drying, tray drying, kettle drying, or spray
hyde resins. Thus, US. 2,769,799 and 2,769,800 to Suen
drying, preferably by the latter method, and the ot-alkyl
et a1. disclose that by reacting melamine, formaldehyde
D-glucoside thcrt incorporated into the dry resinous com
(or a partially polymerized melamine-formaldehyde resin)
position at any time prior to the cure of the composition.
and large amounts of a polyfunctional aliphatic poly
As is well known, aminoplast condensation reactions
amine such as 3,3’-iminobispropylamine (amounts rang
3,082,180
9
10
are influenced by pH, the rate of reaction being acceler
In testing the post-forming characteristics of decora
tive laminates, the procedure prescribed in the NEMA
Standards Publication for laminated thermosetting deco
ated by low pH. At relatively high plei‘s, i.e., signi?cantly
greater than 10, the reaction is slow, while at relatively
rative sheets was employed. More speci?cally, this
method is described in detail in section LP2~2.11 of said
low pI-l’s, the reaction is so fast as to be uncontrollable.
‘At either relatively high or relatively low pH’s, the nature
of the product is such that it has little utility in thermo
setting applications such as laminating and molding resins.
publication. The method consists of employing lami
nated specimens of size 2 inches by 8 inches. A stand
Thus, the practical pl‘l working range for the preparation
ard heater was utilized whereon the test specimen was
of an aminotriazine-aldchyde resin suitable for use in
placed 3 inches above the heating elements. A potential
laminating and molding operations is generally given as 10 across the standard heater was maintained at 120 volts.
from about 6.5 to about 10, although wider and narrower
pH ranges may be employed under certain conditions.
When the specimen reached constant temperature, it was
placed in a bending jig with the decorative face down
The amine component of our novel modi?er system
and formed therein (the NEMA Standards specify that
may be initially added in into to the condensation reaction
the closing time after initial contact of the force with the
mixture. Alternatively, a part of the total amount of 15 specimen is not to exceed 1 second). The specimen with
amine to'be added may be introduced initially and the
the pressure exerted thereon was allowed to form while ,
rest either added in whole or in part during later stages
cooling in the jig for 1 minute. The forming or shaping
of the reaction or blended together with the resinous
portion of the jig consisted of two engageable blocks, the
composition after the condensation reaction has been
lower member of which, upon which the specimen face
carried to the desired stage of completion. This expe 20 was placed, consisted of a stationary and ?xed block of
dient provides an excellent means of controlling the pH
prescribed dimensions ‘having a cavity in the shape of a
ranges at which the reaction is carried out. For example,
90° notch. The top forming block or force was of a
a minor amount of amine may be added to a condensa
male design capable of engaging the notch of the bot-tom
tion reaction mixture comprising aminotriazine, aldehyde,
N-methyloltoluene sulfonamide and optionally, ot-alltyl
block. The bottom extremity of the force consisting of a
longitudinal edge, the cross~sectional area of which cor
responds to an arc of a circle. The ‘radius of the circle
determined the extent to which the specimen was shaped.
D-glucoside, to maintain a slurry pH of from about 7.0
to about 8.5.
When the desired stage of reaction is ac
complished, the pH may again be adjusted with more
.
The standard are prescribed in testing post~forming char
amine to a working pH within the range of from about
acteristics of decorative laminates is that of a circle hav
8.0 to about 9.5 or higher. Of course, any other suitable 30 ing a radius of 3/4 inch.
.
substance, e.g., weakly acidic or basic organic or inor~
The results of the comparative tests are summarized as
ganic solutions, may be employed to adjust the pH when
follows:
required.
‘
Table I
In order that those skilled in the art may more fully
understand the inventive concept presented herein, the fol 35
Minimum Post-Formed
lowing illustrative examples are set forth. These exam
Radius (in inches)
Laminates
Nos.
ples are given by way of illustration and should not be
considered as expressing limitations unless so set forth in
Group I
Group II
the appended claims. All parts and percentages are by
weight, unless otherwise stated.
EXAMPLE I
126 parts of melamine, 183 parts of formaldehyde (as
a 37% aqueous solution), 17.2 parts of toluene sulfon
amide (a mixture of the ortho and para isomers in a
weight ratio of 40:60, respectively), 18.4 parts of 0t
methyl-D-glucoside, and 0.14 part of 3,3’-iminobispropyl
amine (approximately 20% of the total amount tobe
added; su?icient to adjust the slurry pH to 7.8-8.2) were
introduced into a suitable reaction vessel equipped with
thermometer, stirrer, and reflux condenser. The slurry
was heated for 30 minutes to reach re?ux temperature
and held at rellux for an additional 20 minutes. The
resinous composition was, cooled to 60n C., and 0.55
part of 3,3’-iminobispropylamine was blended therewith.
The resulting resin syrup was then cooled to room tem~
perature; it could either be used directly for impregnat
943
%u
6/‘;
%
The laminates of group I, which contain print sheets
impregnated with melamine-formaldehyde resin modi?ed
in accordance with our invention, were all capable of
being post-formed to considerably sharper angles than the
corresponding laminates of group III, which contain only
two of the components found in the three-component
50 modi?er system used in the impregnating resins of the
group I laminates. If the modi?ed resin were used in
the overlay as well as in the print paper, even better post
' '
‘formability would result, e.g., the radius at the apex
would be decreased by as much as another 1A inch. How
ever, some sacri?ce in surface properties would also re~
sult.
EXAMPLE II
126 parts of melamine, 183 parts of 37% aqueous I
ing paper or spray dried by conventional means to yield
a ?nely divided white powder.
00 formaldehyde and 0.14 part of 3,3'-iminobispropy1amine
at a slurry pH of 7.8-8.2 were introduced into a suitable
In order to illustrate the excellent post-forming proper
reaction vessel and heated at 80° C. for one hour. 17.2
ties possessed by decorative laminates containing the novel
modi?edaminoplast resinous compositions of this inven
parts of toluene sulfonamide (40:60—-ortho, para isomer
tion, a series of comparisons were made between decora
mixture) and 18.4 parts of a-methyl-D-glucoside were
tive laminates whose print papers had been impregnated
with the resin of Example I (group I) and laminates
(group 11) prepared in the same manner and identical
then added, and the resinous syrup was further heat re
acted for ‘A: hour at 80° C. The resinous composition
was then cooled to 60° C. and 0.55 part of 3,3’-iminobis
in every respect to those of group I with one exception.
propylarnine blended therewith. The resin syrup, when
cooled to room temperature, could be used directly for
of group H, while containing the same amounts of tolu 70 impregnating paper or could be spray dried.
ene sulfonamide and oz-methyl-D-glucoside as the resin
EXAMPLE III
used in the laminates of group I, did not contain any of
The melamitie-formaldehyde resin used in the laminates
the third essential component of the modifying system
incorporated in the resin of Example 1, namely, ‘3,3’
iminobispropylamine.
A slurry of 126'parts of melamine, 183 parts of 37%
aqueous formaldehyde, 18.4 parts of wmethyl-D-gluco
75 side, 17.2 parts of toluene sulfonamide (40:60—ortho,
3,082,180
11
para isomer mixture) and 0.69 part of 3,3’-iminobis
propylamine, contained in a suitable reaction vessel,
were heated‘ for 30 minutes to reach re?ux temperature
and then held at re?ux for an additional ten minutes.
The resulting resin syrup was allowed to cool to room
12
60% to about 75% by weight of the resinous syrup. On
the other hand, the print sheet, which may be pigmented,
has a thickness of about 6 to 12 mils and is impregnated
with the resin to the extent of about 30% to about 55%
by weight, and preferably from about 35% to about 45%
temperature and was then spray dried to give a ?nely
by weight.
divided White powder.
sheets may be carried out by such methods as dipping,
Impregnation of the cellulosic laminating
roll coating, spraying or the like. The resin impregnated
EXAMPLE IV
sheets may be conveniently dried in a forced hot air oven
2.3 parts of dicthylethanolamine were added to a mix— 10 or by infrared heating means to a volatile content less
ture of 126 parts of melamine, 183 parts of formaldehyde
(as a 37% aqueous solution), 17.2 parts ‘toluene sul
fonamide (40:60-ortho, para isomer mixture), and 18.4
parts of a-methyl-D-glucosidc, and the resulting slurry
heated for a total of 40 minutes (30 minutes to reach re
?ux temperature, 10 minutes at re?ux). After cooling to
room temperature, the resinous syrup was spray dried to
a ?ne white powder.
Conventional laminating techniques may be employed
to prepare thermosetting decorative laminates containing
our novel, modi?ed aminoplast resinous compositions.
than about 6% by weight, and, preferably, in the range
of from about 3% to about 4% by weight. In certain
instances it is desirable to lower the volatile content to
as little as 0.5% by weight, but in this case extreme dry
ing conditions are required. When the cellulosic sheets
impregnated with the novel resinous composition of this
invention are employed with a core assembly impreg
nated with a phenol-formaldehyde condensation product,
the core assembly is usually impregnated in an amount
of about 25% to 35%, preferably about 30% by weight
and dried to a volatile content of less than about 10% by
weight.
After the cellulosie sheets are combined with a
The laminating sheets are ?rst saturated with a solution
core assembly, the total assembly is cured at elevated
or syrup of the resinous material. In view of the novel
temperatures and pressures, e.g., at temperatures within
properties of our resinous compositions, they may be
the range of from about 145° C. to about 165° C. and
25
dissolved or dispersed in entirely aqueous media, but pref
pressures in the order of from about 800 to about 1500
erably a minor amount of alcohol will be added in order
p.s.i., to form the laminate. The laminate, if desired,
to obtain greater ease of solution or dispersion of the
may be buffed to produce glossy or satiny effects thereon.
composition. Thus, the solvent employed may contain
When the laminate is cured between highly polished stain_
80 parts of water and only 20 parts of a water-soluble
alcohol. It is preferred, however, that the solvent utilized 30 less steel platens, it is usually not necessary to buff the
laminate in order to product a glossy effect.
contain as much as 95 parts of water and consequently
It will be obvious that dyes, pigments and other col
only 5 parts of a water-soluble alcohol. The water
orants may also be incorporated into the resinous compo
soluble alcohols utilized are the lower alkyl saturated
sitions to alter the visual appearance and the optical prop
monohydric alcohols, such as methanol, ethanol, propa
nol, isopropanol, n-butanol, isobutanol, and the like. The 35 erties of the finished product. In certain instances it is
desirable to incorporate curing agents, such as p-toluene
dispersion or syrup of the melamine-formaldehyde con
densation product generally contains from about 45% to
about 55% resin solids. In some applications, however,
sulfonic acid, phthalic anhydride, phthalic acid, benzoic
acid and the like into the resinous compositions. in addi
tion to laminates, molded articles may also be prepared,
it may be desirable to reduce the resin solids content to
as low as about 20% and for other applications to as 40 and catalysts, such as phthalic anhydride, as well as mold
lubricants such as zinc stearate, calcium stearate, glycerol
high as about 60%. The amount of the modi?ed resinous
mono-stearate and the like may also be incorporated in
composition employed in the production of the laminates
our novel, modi?ed aminoplast resinous compositions to
may vary from about 30% to about 80% by weight, based
facilitate the molding thereof. The additives herein dis—
on the total weight of the laminate. It is apparent that
cussed may be mixed with the resinous composition at
the amount of the resin present in the laminate will vary,
any point prior to the cure of the material by methods
depending upon the ultimate use of the product and also
well
known in the art.
upon other considerations, as for example the type of
It will be obvious that other changes and variations
laminating sheet being treated. After the laminating
may be made in carrying out the present invention with
sheets are impregnated, they are dried at elevated tem
out departing from the spirit and scope thereof as de?ned
peratures to a desired volatile content. The sheets are
in the appended claims.
then assembled in multiple layers between molding press
We claim:
platens and cured at elevated temperatures and pressures
1. A modified resinous composition of matter which
to form the laminated articles. In decorative laminates,
imparts improved post-forming characteristics to decora
the decorative print sheet alone can be impregnated with
the modi?ed resin, or, as previously mentioned, both 55 tive laminates prepared therefrom which comprises an
aminotriazine-aldehyde resin having a mol ratio of alde
the overlay and the decorative print sheets may be im
hyde to aminotriazine of ‘from about 1.5:1 to about 6:1,
pregnated. For economical reasons, the core assembly
respectively, the aminotriazine component of which ini
is usually impregnated with a different and cheaper ther~
tially contains -at least two amidogen groups each having
mosetting resin, as for example a phenol-formaldehyde
condensation product. In industrial laminates wherein the 60 at least one aldehyde~reactable hydrogen atom attachedv
to the amidogen nitrogen atom, modi?ed with (1) an a
sheets are usually of the same material, all of the sheets
alkyl-D-glucoside, (2) an N-methylol sulfonamide, the
may be treated with the modi?ed aminoplast resin. Sheets
total amount of said (1) vand said (2) present being from
of ?brous material, such as a-cellulose, paper, viscose
about 1% to about 35% by weight, based on the total
rayon paper, glass cloth, or cloth formed of silk, cotton,
wool, rayon or other synthetic ?bers, may be utilized in 65 weight of the modi?ed resinous composition, and from
about 0.1% to about 1.5% by weight, based on the total
the preparation of the laminated articles.
weight of the modi?ed resinous composition of (3) an
The resinous syrups of the present invention are prefer
alkylene polyamine.
ably employed to impregnate a-cellulose or eellulosic sat
2. A modi?ed resinous composition of matter which
urating sheets which are employed in the production of
decorative laminated articles. In this instance, the cel 70 imparts improved post-forming characteristics to decora
tive laminates prepared therefrom which comprises an
lulosic sheets are combined with a core assembly impreg~
aminotriazine-aldehyde resin having a mol ratio of alde
natcd with a phenol-formaldehyde condensation product
hyde to aminotriazine of from about l.5:l to about 6:1,
and then cured under heat and pressure to form the lam
respectively, the aminotriazine component of which ini
inated article. A decorative overlay sheet having a thick
ness of about 2 to 5 mils is impregnated with from about 75 tially contains at least two amidogen groups each having
3,082,180
13
at least one aldehyde-reactable hydrogen atom attached to
the amidogen nitrogen atom, modi?ed with (1) an a
ialkyl-D-glucoside, (2) an N-methylol sulfonamide, vthe
total amount of said (1) and said (2) present being from
about 1% to about 35% by weight, based on the total
weight of the modi?ed resinous composition, and from
about 0.1% to about 1.5% by weight, based on the total
weight of the modi?ed resinous composition of (3) a
polyalkylene polyamine.
_
3. A modi?ed resinous composition of ‘matter which
imparts improved post~forming characteristics to decora
tive laminates prepared therefrom which comprises an
aminotriazine~aldehyde resin having 2. mol ratio of alde
hyde to aminotriazine of from about 1.5:1 to about 6:1, '
respectively, the aminotriazine component of which ini
tially contains at least two amidogen groups each having
at least one [aldehyde-readable hydrogen atom attached
to the atrnidogen nitrogen atom, modi?ed with (l) a
methyl-D-glueosidc, (2) N-methylol p-toluene sulfon
14
polyamine present to within the range of from about
0.1% to about 1.5% by weight, based on total weight of
the modi?ed resinous composition, and (4) recovering
the resulting modi?ed resinous composition.
7. A process for the preparation of a modi?ed resinous
composition of matter which imparts improved post-form
ing characteristics to decorative laminates prepared there
from which comprises: ( 1) heating at temperatures
ranging from about 40° C. to about 100° C. for from
about 30 to 120 minutes a mixture comprising (A) mc1~
amine, (B) formaldehyde, the mol ratio of said (B) to
said (A) being from about 1.5:1 to about 6:1, respec
tively, (C) u-methyLD-glucoside, (D) N-methylol p-tol
uene sulfonamide, the total amount of said (C) and said
(D) present being from about 1% to about 35% by
weight, based on the total weight of the modified resinous
composition, and (B) an amount of 3,3’-iminobispropyl
amine su?icient to maintain the pH of the mixture within
amide, the total amount of said (1) and said (2) present H ‘the range of from about 7.0 to about 8.5, to form a
resinous syrup, (2) cooling said syrup to at least 60° C.,
being from about 1% to about 35 % by weight, based on
(3) adding to said cooled syrup an additional amount of
the total weight of the modi?ed resinous composition,
3,3’-iminobispropylamine su?icient to bring the total
and from about 0.1% to about 1.5% by weight, based
amount of 3,3'-iminobispropylamine present to within the
on the total weight of the modi?ed resinous composi
range of from about 0.1% to about 1.5% by weight,
tion of (3) an alkylene polyamine.
based on total weight of the modi?ed resinous composi
4. A modi?ed resinous composition of matter which
imparts improved post-forming characteriistics to decora
tive laminates prepared therefrom which comprises an
aminotriazine-aldehyde resin having a mole ratio of alde
hyde to aminotriazine of from about 1.5:1 to about 6:1,
respectively, the aminotriazine component of which ini
tially contains at least two amidogen groups each having
at least one aldehyde-reaetable hydrogen atom attached
to the am-idogen nitrogen atom, modi?ed with (1) a
methyl—D-glucoside, (2) N-methylol p-toluene sulfon- 3
amide, the total amount of said (1) and said (2) present
being from about 1% to about 35 % by weight, based on
the total weight of the modi?ed resinous composition, and
from about 0.1% to about 1.5% by weight, based on the
tion, and (4) recovering the resulting modi?ed resinous
composition.
8. A process for the preparation of a modi?ed resinous
composition of matter which imparts improved post-form
ing characteristics to decorative laminates prepared
therefrom which comprises: (1) heating at temperatures
ranging from about 40° C. to about 100° C. for from
about 30 to 120 minutes a mixture comprising (A) an
aminotriazine having at least two amidogen groups, each
having at least one aldehyde-reactable hydrogen atom
attached to the amidogcn nitrogen atom, (B) an aldehyde,
the mol ratio of said (B) to said (A) being from about
1.5 :1 to about 6:1, respectively, (C) an a~alkyl-D-glu~
total weight of the modi?ed resinous composition of (3) ' 40 coside and (D) an N-methylol sulfonamide, the total
a polyalkylene polyamine.
‘amount of said (C) and said (D) present being from
5. A modi?ed resinous composition of matter which
‘about 1% to about 35% by weight, based on the total
imparts improved post-forming characteristics to decora
weight of the modi?ed resinous composition, to form a
tive laminates prepared therefrom which comprises a
resinous syrup, (2) cooling said syrup to at least 60° C.,
melamine-formaldehyde resin having a mol ratio of 45 (3) adding an amount of an alkylene polyamine within
formaldehyde ‘to melamine of from about 1.5 :1 to about
the range of from about 0.1% to about 1.5 % by weight,
6: 1, respectively, modi?ed with (1) a-rnethyl-D-glucoside,
based on the total weight of the modi?ed'composition,
(2) N-methylol p-toluene sulfonamide, the total amount
of said ( 1) and said (2) present being from about 1%
to about 35% by weight, based on the total weight of
the modi?ed resinous composition and from about 0.1%
to about 1.5% by weight, based on the total weightof the
modi?ed resinous composition of (3) 3,,3’-iminobispro
pylamine.
'
6. A process for the preparation of a modi?ed resinous
composition of matter which imparts improved post
' forming charcteristics to decorative laminates prepared‘
- ‘therefrom which comprises: (1) heating at temperatures
and (4) recovering the resulting modi?ed resinous com
position.
‘
9. A process for the preparation of a modi?ed resinous
composition of matter which imparts improved post-form
ing characteristics to decorative laminates prepared there
from which comprises: (‘11) heating at temperatures rang—
ing from about 40° C. to about 100° C. for from about
30 to 120 minutes a mixture comprising (A) melamine,
(B) formaldehyde, the mol ratio of said (13) to said (A)
being from about 1.5:1 to about 6:1, respectively, (C)
a-methyl-D-glucoside and (D) N-methylol p~toluene sule
ranging from about 40° C. to about 100° C. for from
fonamide, the total amount of said (C) and said (D)
about 30 to 120 minutes a mixture comprising (A) an
60
present being from about 1% to about 35% by weight,
aminotriazine having at least two amidogen groups, each
having at least one aldehyde-reactable hydrogen atom
based on the total weight of the modi?ed resinous com
attached to the amidogen nitrogen atom, (B) an alde
position, to form a resinous syrup, (2) cooling said syrup
hyde, the mol ratio of said (B) to'said (A) being from
to at least 60° C., (3) adding an amount of 3,3'~iminobis—
about 1.5 :1 to about 6:1, respectively, (C) an a-alkyl-D
propylamine within the range of from about 0.1% to
glucoside (D) an N-methylol sulfonamide, the total
about 1.5% by weight, based on the total weight of the
amount of said (C) and said (D) present being from
modi?ed composition, and ,(4) recovering the resulting
‘about 1% to about 35% by weight, based on the total
modi?ed resinous composition.
weight of the modi?ed resinous composition, and (E)
an amount of an alkylene polyamine sufficient to main
tain the pH of the mixture within the range of from 70
> about 7.0 to about 8.5, to form a resinous syrup, (2)
cooling said syrup to at least 60° C., (3) adding to said
cooled syrup an additional amount of an alkylene poly
amine sufficient to bring the total amount of alkylene 75
References Cited in the'?le of this patent
UNITED STATES PATENTS
2,769,800
Suen et al _____________ __ Nov. 6, 1956
2,773,788 ‘
Magrane et a1 _________ “ Dec. 11, 1956
2,796,362
Wooding et al. .. _______ _._ June 18, 1957
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